Sorbent with a great quantity of highly dispersed active components is of importance to achieve excellent desulfurization performance. Thus, Zn@MnOx/porous carbon nanofibers (PCNFs) sorbents have been constructed via electrospinning, carbonization, activation and hydrothermal techniques in this study. The as-prepared sorbent realizes a sulfur capacity of 9.63 g S 100 g-1 sorbent and a utilization rate 117% of ZnO, which could be attributed to the synergetic effects of the enlarged surface area of PCNFs and uniformly distributed active components. The specific surface area of modified PCNFs is nearly five times higher than that of the pristine CNFs, providing larger loading area and more attachment sites for metal oxides. Activation with KMnO4 not only generates active MnOx components but also presets ‘seed’ for ZnO crystals growth, which is beneficial for the high dispersion of nano-sized active components. The presented method is beneficial to producing sorbents with better structure and promoted desulfurization performance.